85107-38-6Relevant articles and documents
Activation of Aryl Carboxylic Acids by Diboron Reagents towards Nickel-Catalyzed Direct Decarbonylative Borylation
Deng, Xi,Guo, Jiandong,Su, Weiping,Wang, Xiaotai,Zhang, Xiaofeng
supporting information, p. 24510 - 24518 (2021/08/12)
The Ni-catalyzed decarbonylative borylation of (hetero)aryl carboxylic acids with B2cat2 has been achieved without recourse to any additives. This Ni-catalyzed method exhibits a broad substrate scope covering poorly reactive non-ortho-substituted (hetero)aryl carboxylic acids, and tolerates diverse functional groups including some of the groups active to Ni0 catalysts. The key to achieve this decarbonylative borylation reaction is the choice of B2cat2 as a coupling partner that not only acts as a borylating reagent, but also chemoselectively activates aryl carboxylic acids towards oxidative addition of their C(acyl)?O bond to Ni0 catalyst via the formation of acyloxyboron compounds. A combination of experimental and computational studies reveals a detailed plausible mechanism for this reaction system, which involves a hitherto unknown concerted decarbonylation and reductive elimination step that generates the aryl boronic ester product. This mode of boron-promoted carboxylic acid activation is also applicable to other types of reactions.
Metal-Free Radical Borylation of Alkyl and Aryl Iodides
Cheng, Ying,Mück-Lichtenfeld, Christian,Studer, Armido
, p. 16832 - 16836 (2018/11/23)
A metal-free radical borylation of alkyl and aryl iodides with bis(catecholato)diboron (B2cat2) as the boron source under mild conditions is introduced. The borylation reaction is operationally easy to conduct and shows high functional group tolerance and broad substrate scope. Radical clock experiments and density functional theory calculations provide insights into the mechanism and rate constants for C-radical borylation with B2cat2 are disclosed.
Chelate restrained boron cations for intermolecular electrophilic arene borylation
Del Grosso, Alessandro,Pritchard, Robin G.,Muryn, Chris A.,Ingleson, Michael J.
, p. 241 - 249 (2010/04/04)
Highly electrophilic boron species that borylate arenes are generated by halide abstraction from CatBX (Cat = catecholato, C6H 4O22-, X = Cl or Br) by [Et3Si] [CbBr6] (CbBr6 = [closo-1-H-CB11H 5Br6]-). A transient [CatB][CbBr6] related species reacts as a synthetic equivalent of [CatB]+ in intermolecular electrophilic borylation, with reactions proceeding rapidly at 25 °C. The [CatB]+ moiety was shown to be strongly Lewis acidic on the basis of 1H and 31P{1H} NMR spectroscopy of the crotonaldehyde and triethylphosphine oxide adducts, respectively. Catalytic quantities of [Et3Si][CbBr6] and CatBX were effective for the high-yielding borylation of arenes by CatBH in a highly atom efficient cycle with H2 the only byproduct. Successful catalysis was dependent on the robust [CbBr6]- anion and the use of electrophile-resistant borane sources